U.S. patent application number 17/610500 was filed with the patent office on 2022-08-04 for microparticle compositions comprising saflufenacil.
The applicant listed for this patent is BASF AGRO B.V.. Invention is credited to Katharine Klamczynski, Wolfgang Laik, Ulrich Steinbrenner, Joerg Steuerwald.
Application Number | 20220240507 17/610500 |
Document ID | / |
Family ID | |
Filed Date | 2022-08-04 |
United States Patent
Application |
20220240507 |
Kind Code |
A1 |
Steinbrenner; Ulrich ; et
al. |
August 4, 2022 |
MICROPARTICLE COMPOSITIONS COMPRISING SAFLUFENACIL
Abstract
A microparticle composition comprising saflufenacil, wherein
saflufenacil is present in the form of microparticles, which
comprise solid saflufenacil, which is surrounded or embedded by an
aminoplast polymer, which is a polycondensation product of one or
more amino compounds and one or more aldehydes, and further
comprising at least one lignin based sulfonic acid A, such as
lignosulfonic acid, ethoxylated lignosulfonic acid or oxidized
lignins, wherein said lignosulfonic acid A has an average molar
weight MW of at least 10,000 Da.
Inventors: |
Steinbrenner; Ulrich;
(Ludwigshafen, DE) ; Steuerwald; Joerg;
(Limburgerhof, DE) ; Klamczynski; Katharine;
(Limburgerhof, DE) ; Laik; Wolfgang; (Neustadt,
DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF AGRO B.V. |
Arnhem |
|
NL |
|
|
Appl. No.: |
17/610500 |
Filed: |
May 27, 2020 |
PCT Filed: |
May 27, 2020 |
PCT NO: |
PCT/EP2020/064626 |
371 Date: |
November 11, 2021 |
International
Class: |
A01N 43/54 20060101
A01N043/54; A01N 25/10 20060101 A01N025/10; A01P 13/00 20060101
A01P013/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 7, 2019 |
EP |
19179063.3 |
Claims
1. A microparticle composition comprising saflufenacil, wherein
saflufenacil is present in the form of microparticles, which
comprise solid saflufenacil, which is surrounded or embedded by an
aminoplast polymer, which is a polycondensation product of one or
more amino compounds and one or more aldehydes, and further
comprising at least one lignin based sulfonic acid A, wherein said
lignosulfonic acid A has an average molar weight MW of at least
10,000 Da and a degree of sulfonation from 1.0 to 2.5 mol per
kilogram of said lignosulfonic acid A, and wherein the aminoplast
polymer is selected from the group consisting of melamine
formaldehyde resins, urea formaldehyde resins, and mixtures
thereof.
2. The composition of claim 1, wherein said at least one lignin
based sulfonic acid A is selected from the group consisting of
lignosulfonic acid and ethoxylated lignosulfonic acid.
3. The composition of claim 1, further comprising at least one
anionic surfactant A2, anionic surfactant A2 being homo- or
copolymers of monoethylenically unsaturated monomers M1 having a
sulfonic acid group optionally with one or more comonomers M2
different from monomers M1.
4. The composition of claim 1, further comprising an alkyl
sulfate.
5. The composition of claim 1, wherein the aminoplast polymer is a
melamine formaldehyde resin.
6. The composition of claim 1, wherein an amount of aminoplast
polymer in the microparticle composition is from 0.5 to 40% by
weight, based on the total weight of aminoplast polymer and
saflufenacil.
7. The composition of claim 1, wherein the microparticles have a
weight average particle diameter d50 in the range from 1 to 25
.mu.m, as determined by dynamic light scattering of an aqueous
dispersion of the microcapsules.
8. The composition of claim 1, wherein the microparticles comprise
less than 10% by weight of particles having a particle diameter of
more than 50 .mu.m, as determined by dynamic light scattering of an
aqueous dispersion of the microcapsules.
9. The composition of claim 1, which is an aqueous suspension of
the microparticles.
10. The composition of claim 1, which is solid composition of the
microparticles.
11. The composition of claim 1, which contains one or more
auxiliaries conventionally employed for the formulation of plant
protection compositions.
12. A method for producing the composition of claim 1 comprising:
i) providing an aqueous suspension or dispersion of solid
saflufenacil particles; ii) adding an aminoplast pre-condensate to
the aqueous suspension; iii) effecting the polycondensation of the
aminoplast pre-condensate.
13. The method of claim 12, where the saflufenacil particles in the
aqueous suspension dispersion have a weight average particle
diameter d50 in the range from 0.5 to 25 .mu.m, as determined by
dynamic light scattering.
14. (canceled)
15. A method of controlling undesired vegetation, wherein a
microparticle composition of claim 1 is allowed to act on plants,
their environment and/or on seeds.
16. The composition of claim 6 wherein the amount of aminoplast
polymer in the microparticle composition is from 1 to 35% by
weight, based on the total weight of the aminoplast polymer and
saflufenacil.
17. The composition of claim 6 wherein the amount of aminoplast
polymer in the microparticle composition is from 5 to 25% by
weight, based on the total weight of the aminoplast polymer and
saflufenacil.
Description
[0001] The present invention relates to microparticle compositions
comprising saflufenacil, to a method of their preparation and to
the use of these microparticle compositions for controlling
undesired vegetation.
[0002] Saflufenacil is the INN common name of the herbicidally
active phenyl uracil compound
2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1-(2H)pyri-
midinyl]-4-fluoro-N-[[methyl(1-methylethyl)amino]sulfonyl]benzamide.
[0003] Saflufenacil has been described for the first time in WO
01/083459.
[0004] Saflufenacil is a highly active herbicide which efficiently
inhibits growth of undesirable vegetation at low application rates.
Unfortunately, its selectivity is not always satisfactory and its
use in crops is somewhat limited. Moreover, the saflufenacil does
not have sufficient residual activity and thus regrowth may occur
shortly after it has been applied.
[0005] Herbicides, such as saflufenacil, are normally applied in
the form of dilute aqueous spray liquors, which are prepared by
diluting a concentrate formulation of the herbicide with water. For
this purpose, pesticide compounds may be formulated in solid forms,
such as wettable powders (WP) and water-dispersible granules (WG),
as well as in liquid forms, such as emulsions, emulsifiable
concentrates (EC), suspoemulsions (SE) or suspension concentrates
(SC). For efficient encapsulation, it is of particular importance
that the formulations can be easily diluted with water and that the
dilution remains stable for a certain time without separation of
the active ingredient, as this may cause clogging of the spraying
nozzles. For ecological reasons it is preferred that the
formulation does not contain large amounts of organic solvents,
which principally favors solid formulations and aqueous SC
formulations.
[0006] Despite the aforementioned advantages associated with the
usage of SCs, there are a number of problems known to the skilled
person which are sometimes encountered with SCs as a result of
settling during prolonged storage or storage at elevated
temperatures, the resistance of settled particles to re-suspension
and the formation of crystalline material upon storage. As a
consequence, the formulations may be difficult to handle and the
bioefficacy may be inconsistent.
[0007] When trying to formulate saflufenacil one faces several
problems. Saflufenacil carries a N-amino-sulfonylcarboxamide
side-chain which might undergo hydrolysis at basic pH values. Apart
from that, saflufenacil is capable of existing in different
crystalline and non-crystalline modifications, namely amorphous
forms, crystalline hydrates and a crystalline anhydrate, which may
undergo uncontrolled conversion into another crystalline form. This
conversion in turn may lead to coarsening of the saflufenacil
particles, in particular when formulated as suspension concentrate.
These factors might result in a reduced chemical and physical
stability of the formulations, an effect that is particularly
pronounced when the formulations are stored over prolonged periods
of time and/or at elevated temperatures. Said factors may also lead
to poor dilution properties as the coarse saflufenacil particles
are prone to separate from the diluted formulation.
[0008] Several stable aqueous agricultural formulations of
saflufenacil have been described so far. WO 2011/023759 describes
an aqueous suspension concentrate formulation containing
saflufenacil-anhydrate and a combination of certain anionic and
non-ionic surfactants. WO 2011/023758 describes an aqueous
suspension concentrate formulation of saflufenacil which
additionally contains glyphosate as a co-herbicide.
[0009] Although, these formulations are stable, they do not solve
the problem of poor crop selectivity and insufficient residual
activity.
[0010] It is principally known to provide pesticidally active
compounds in the form of microcapsule formulations (see H. Mollet,
A. Grubenmann "Formulation Technology" 1st ed., Wiley-VCH Verlag
GmbH, Weinheim 2001, Chapter 6.4 and Chapter 14.2.2).
Microencapsulation can be principally achieved by coacervation
techniques, spray drying, fluidized-bed coating, electrostatic
microencapsulation or in-situ polymerization. These techniques
provide active compound particles, wherein the active compound is
surrounded by a polymeric wall material.
[0011] WO 2017/037210 discloses microparticle compositions of
saflufenacil.
[0012] Although microencapsulation may improve the acute toxicity
of a pesticide or reduce degradation, it is often difficult to
achieve. In particular, aggregation of the pesticide particles
during or after encapsulation is the main problem, if one
encapsulation method, which may work for a particular pesticide
compound, does not necessarily work for another pesticide compound.
When trying to encapsulate a solid material in an aqueous
suspension of the solid material by an in-situ-polymerization
technique, the solid material tends to agglomerate thereby forming
large particles of active ingredient particles, which are embedded
in the polymer matrix. A thus obtained suspension is usually no
longer suitable for agricultural use. So fat, it was not possible
to efficiently encapsulate solid pesticide particles by using small
amounts of an encapsulating polymer.
[0013] One challenge of known formulations of saflufenacil is to
increase the compatibility with other pesticides.
SUMMARY OF INVENTION
[0014] It is an object of the present invention to provide a
formulation of saflufenacil that is compatible with a broad range
of other pesticides, especially other tank mix partners which are
commonly combined with saflufenacil, such as glyphosate,
glufosinate, dicamba etc. . . . Furthermore, it should show both
high physical and chemical stability over prolonged storage periods
while maintaining its biological efficacy. Moreover, it should also
be compatible with tank-mix partners which are commonly combined
with saflufenacil. Upon dilution with water, the formulation should
give a stable aqueous composition of saflufenacil without forming
coarse material or a supernatant liquid. It was surprisingly found
that the objective could be achieved by microparticle compositions
of solid saflufenacil, wherein solid saflufenacil is surrounded or
embedded by an aminoplast polymer, and further comprising at least
one lignin based sulfonic acid A, such as lignosulfonic acid,
ethoxylated lignosulfonic acid or oxidized lignins, wherein said
lignosulfonic acid A has an average molar weight MW of at least
10,000 Da.
[0015] In the microparticle compositions of the present invention,
saflufenacil is less prone to degradation. Thus, the microparticle
compositions of the present invention provide for both high
physical and chemical stability over prolonged storage periods,
while maintaining the biological efficacy of saflufenacil.
Moreover, microparticle compositions of the present invention can
be easily formulated. Furthermore, microparticle compositions of
the present invention in the form of aqueous suspensions provide
for improved tank-mix compatibility, and thus can be readily tank
mixed with other formulations of pesticides and do not negatively
interact with other formulations regarding their dilution
stability.
[0016] It was also surprisingly found that solid saflufenacil can
be efficiently microencapsulated by using aminoplast
pre-condensates and performing the process described hereinafter.
Therefore, a second aspect of the present invention relates to a
process for preparing the microparticle compositions as described
herein, which process comprises the following steps: [0017] i)
providing an aqueous suspension of solid saflufenacil particles;
[0018] ii) adding an aminoplast pre-condensate to the aqueous
suspension of the saflufenacil particles; [0019] iii) effecting the
polycondensation of the aminoplast pre-condensate, e.g. by heating
the aqueous suspension of step ii) at a pH, where the
polycondensation of the aminoplast pre-condensate will occur at the
reaction temperature.
[0020] This process results in a stable aqueous suspension, wherein
saflufenacil is present in the form of microparticles, which
comprise solid saflufenacil, which is surrounded or embedded by an
aminoplast polymer. From this, the microparticles can be isolated,
if necessary. Surprisingly, this process does not result in
significant agglomeration of the saflufenacil particles, as was
observed for other in-situ polymerization techniques.
DETAILED DESCRIPTION OF INVENTION
[0021] In the microparticle composition of the invention
saflufenacil is present in the form of microparticles, which
comprise solid saflufenacil as a core material, said composition
further comprising at least one lignin based sulfonic acid A, such
as lignosulfonic acid, ethoxylated lignosulfonic acid or oxidized
lignins, wherein said lignosulfonic acid A has an average molar
weight MW of at least 10,000 Da. In the microparticles solid
saflufenacil forms the core material which is surrounded or
embedded by at least one aminoplast polymer. In this context, it
has to be understood that the aminoplast polymers may form a
regular or irregular shell which surrounds or embeds the core
material. The microparticles may have a single solid core formed by
the saflufenacil and a shell or matrix formed by the aminoplast
polymer. It may, of course, also be possible that the
microparticles have a "domain structure" which comprises a certain
number of solid saflufenacil particles, e.g. 3 to 1000 or 10 to
500, of amorphous or crystalline saflufenacil, which are embedded
by the aminoplast polymer.
[0022] It is not necessary that the aminoplast polymer forms a
completely closed shell. Frequently, however, the shell will
completely surround the core material like a membrane, thereby
forming a barrier between the core material and the surrounding
material.
[0023] Aminoplast polymers, which are also termed amino resins,
amino condensation resins or amido resins are polycondensation
products of one or more aldehydes, such as formaldehyde,
acetaldehyde, propanal, glyoxal or glutaraldehyde, with one or more
amino compounds having usually at least two primary amino groups,
such as urea, thiourea, melamine, which may be wholly or partially
etherified, cyanoguanamine (=dicyandiamide) and benzoguanamine.
Examples of aminoplast polymers are polycondensates of melamine and
formaldehyde (melamine-formaldehyde resins or MF resins), including
resins derived from wholly or partially etherified melamine
formaldehyde condensates, urea-formaldehyde resins (UF resins),
thiourea formaldehyde resins (TUF resins), polycondensates of
melamine, urea and formaldehyde (MUF resins), including resins
derived from wholly or partially etherified
melamine-ureaformaldehyde condensates, polycondensates of melamine,
thiourea and formaldehyde (MTUF resins, including resins derived
from wholly or partially etherified melaminethiourea-formaldehyde
condensates, urea-glutaraldehyde resins, benzoguanamineformaldehyde
polycondensates, dicyandiamide formaldehyde polycondensates and
urea-glyoxal polycondensates. Suitable aminoplast polymers for
microencapsulation are known and can be found, inter alia, in
Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd edition, Vol.
2, pp. 440-469, the prior art cited in the introductory part, U.S.
Pat. No. 4,918,317, EP 26914, EP 218887, EP 319337, EP 383,337, EP
415273, DE 19833347, DE 19835114 and WO 01/51197. In UF and TUF
resins, the molar ratios of urea or thiourea to formaldehyde are
generally in the range from 1:0.8 to 1:4, in particular from 1:1.5
to 1:4, especially from 1:2 to 1:3.5. If glutaraldehyde is used
instead of formaldehyde, the molar ratios of urea or thiourea to
glutaraldehyde may in particular be in the range from 1:1.2 to 1:3,
especially in the range from 1:1.5 to 1:2.5.
[0024] In MF and MUF resins, the molar ratios of melamine to
formaldehyde are generally in the range from 1:1.5 to 1:10, in
particular from 1:3 to 1:8 preferably 1:4 to 1:6.
[0025] In MUF and MTUF resins, the molar ratios of melamine+urea or
thiourea to formaldehyde are generally in the range from 1:0.8 to
1:9, in particular from 1:2 to 1:8; preferably 1:3 to 1:6. The
molar ratio of urea or thiourea to melamine may be in the range
from 50:1 to 1:100 and in particular from 30:1 to 1:30.
[0026] In the preparation of the aforementioned aminoplast resins,
the pre-condensates may be used in the form of etherified
pre-condensates of amino compound and aldehyde. In these etherified
pre-condensates the methylol groups formed by the reaction of the
amino groups with formaldehyde with an alkanol or an alkane diol,
in particular with a C1-C4-alkanol, such as methanol, ethanol,
n-propanol or n-butanol, in particular methanol, or a
C2-C4-alkandiol, such as ethylene glycol. The degree of
etherification of these resins can be adjusted by the molar ratio
of amino groups to alkanol which is typically in the range from
10:1 to 1:10, preferably in the range from 2:1 to 1:5.
[0027] The aminoplast polymer material, which surrounds or embeds
the solid saflufenacil, is most preferably selected from the group
consisting of melamine-formaldehyde resins, including
melamine-formaldehyde resins derived from wholly or partially
etherified melamine-formaldehyde condensates, and urea-formaldehyde
resins and mixtures thereof. Especially, the aminoplast polymer
material, which surrounds or embeds the solid saflufenacil, is a
melamine-formaldehyde resin, in particular a melamine formaldehyde
resin, which is derived from wholly or partially etherified
melamine formaldehyde condensates, which may contain small amount,
e.g. 1 to 20 mol.-%, based on melamine, of urea.
[0028] In the microparticle compositions of the invention, the
amount of aminoplast polymer material, which surround or embed the
solid saflufenacil, will generally not exceed the amount of
saflufenacil contained in the composition and is preferably at most
40% by weight, in particular at most 35% by weight and especially
at most 30% by weight or at most 25% by weight, based on the total
amount of saflufenacil and aminoplast polymers. The amount of
aminoplast polymer material, which surround or embed the solid
saflufenacil, is preferably from 0.5 to 40% by weight, in
particular from 1 to 35% by weight and especially from 5 to 25% by
weight, based on the total capsule weight, i.e. based on the total
amount of saflufenacil and aminoplast polymers. The polymer
material of the microparticle composition of the invention, which
surrounds or embeds the solid saflufenacil, may comprise further
water-insoluble polymers. However, the amount of such polymers will
generally not exceed 20% of the total amount of encapsulating
polymer material and will preferably not exceed 10% by weight of
the total amount of polymer material, which surrounds or embeds the
solid saflufenacil.
[0029] The solid saflufenacil, which is surrounded or embedded by
at least one aminoplast polymer, may be any known form of solid
saflufenacil, including amorphous saflufenacil and in particular
crystalline saflufenacil, e.g. the crystalline anhydrate of
saflufenacil as described in WO 08/043835 or a crystalline hydrate
of saflufenacil as described in WO 08/043836.
[0030] In addition to the solid saflufenacil, the core material of
the microparticles may contain an oil, e.g. a hydrocarbon solvent,
such as an aromatic, paraffinic or isoparaffinic hydrocarbon,
having preferably a boiling point above 100.degree. C., a vegetable
oil, such as corn oil, rapeseed oil, or a fatty acid ester, such as
C1-C10-alkylester of a C10-C22-fatty acid, in particular methyl or
ethyl esters of vegetable oils. such as rapeseed oil methyl ester
or corn oil methyl ester. In a particular embodiment, the core
material does not contain an oil as defined herein or less than 10%
by weight, based on the weight of the core material, of an oil. In
particular, the core does not contain an oil.
[0031] In addition to the solid saflufenacil, the core material of
the microparticles may further contain a further pesticide
compound, in particular a herbicide compound or a safener, having
preferably a reduced water solubility, which generally does not
exceed 10 g/l, in particular 5 g/l or even 1 g/l at 25.degree. C.
(deionized water). In particular, solid saflufenacil makes up at
least 80%, in particular at least 90% of the pesticides contained
in the microparticles.
[0032] The microparticles of the present invention are discrete
particles having usually a particle size of less than 50 .mu.m.
Preferably, the particle size of the microparticles, i.e. their
diameter, will in general not exceed 40 .mu.m, preferably not
exceed 35 .mu.m and in particular not exceed 30 .mu.m. The particle
size given is the so called d90-value, which has to be understood
as the value that is not exceeded by the diameters of at least 90%
by weight of the microparticles. The microparticles have an average
particle diameter, herein also termed d50-value, ranging from 1 to
25 .mu.m, in particular from 1.5 to 20 .mu.m, especially from 2 to
10 .mu.m. The d50-value is defined as the value that is above the
diameters of 50% by weight of the particles and below the diameters
of 50% by weight of the particles. The d90 value as well as the d50
value can be calculated from the particle size distribution of the
microparticles. Generally, the d10-value of the particles, i.e. the
value of diameters which at least 10% by weight of the
microparticles exceed, will be at least 0.5 .mu.m and may e.g. be
in the range from 0.5 .mu.m 10 .mu.m, in particular from 1 to 5
.mu.m. The particle size distribution of the microparticles (i.e.
the diameters) can be determined by conventional methods such as
dynamic or static light scattering of an aqueous dispersion of the
microparticle composition, e.g. at 25.degree. C. and a
concentration in the range of 0.1 to 1% by weight.
[0033] Microparticle compositions according to the invention
contain at least one anionic polymeric surface-active substance A1,
hereinafter also referred to as anionic polymeric surfactant A1 or
polymeric surfactant A1, said at least one anionic polymeric
surface-active substance A1 being a lignin based sulfonic acid A,
wherein said lignin based sulfonic acid A1 has an average molar
weight MW of at least 10,000 Da. Preferably, said lignin based
sulfonic acid A1 has an average molar weight MW of 10,000 Da to
100,000 Da.
[0034] Preferably, said lignin based sulfonic acid A1 has a degree
of sulfonation from 1.0 to 2.5 mol per kilogram of said
lignosulfonic acid.
[0035] The average molar weight MW of said lignin based sulfonic
acid as applied herein is determined by gel permeation
chromatography according to DIN 55672-3.
[0036] The degree of sulfonation said lignin based sulfonic acid as
applied herein is calculated from the sulfur content of said lignin
based sulfonic acid as determined by atomic emission spectroscopy,
from which the content of sulfate (determined according to DIN
38405-D5-2) is being subtracted.
[0037] Preferred lignin based sulfonic acids A1, are lignosulfonic
acid, ethoxylated lignosulfonic acid or oxidized lignins.
[0038] Preferred lignin based sulfonic acids A1, are lignosulfonic
acid, ethoxylated lignosulfonic acid or oxidized lignins.
[0039] In one embodiment, microparticle compositions according to
the invention contain at least one anionic polymeric surface-active
substance A2, surface-active substance A2 being homo- or copolymers
of monoethylenically unsaturated monomers M1 having a sulfonic acid
group optionally with one or more comonomers M2 different from
monomers M1.
[0040] The anionic groups in these anionic polymeric surfactants
may be partially or fully neutralized. Suitable counter ions are
alkali metal ions, such as sodium, potassium, earth alkaline ions
such as magnesium or calcium, and ammonium. In case of anionic
polymeric surfactants having a sulfonate group, the anionic groups
are preferably at least partly neutralized.
[0041] Preferably, the polymeric surfactant A2 is selected from
homo- and copolymers made of [0042] i) at least one
monoethylenically unsaturated monomer M1 having a sulfonic acid
group, such as vinylsulfonic acid, allylsulfonic acid, styrene
sulfonic acid, vinyltoluene sulfonic acid, (meth)acrylate monomers
having a sulfonic acid group, such as 2-acryloxyethylsulfonic acid,
2-acryloxypropylsulfonic or 4-acryloxybutylsulfonic acid, and
(meth)acrylamide monomer having a sulfonic acid group, such as
2-acrylamidoethylsulfonic acid, 2-acrylamidopropylsulfonic acid or
2-acrylamido-2-methylpropane sulfonic acid [0043] ii) and
optionally one or more monoethylenically unsaturated comonomers M2
different from monomers M1, such as styrene, C1-C4-alkylacrylates,
C1-C4-alkylmethacrylates, acrylamide, methacrylamide, acrylic acid,
methacrylic acid, C1-C4-alkylacrylates,
C1-C4-alkylmethacrylates.
[0044] In one embodiment, polymeric surfactant A2 is selected from
homo- and copolymers made of [0045] i) monomers M1, which are
selected from (meth)acrylate monomers having a sulfonic acid group,
such as 2-acryloxyethylsulfonic acid, 2-acryloxypropylsulfonic or
4-acryloxybutylsulfonic acid, and (meth)acrylamide monomer having a
sulfonic acid group, such as 2-acrylamidoethylsulfonic acid,
2-acrylamidopropylsulfonic acid or 2-acrylamido-2-methylpropane
sulfonic acid, [0046] ii) and optionally one or more
monoethylenically unsaturated comonomers M2 different from monomers
M1, such as styrene, C1-C4-alkylacrylates,
C1-C4-alkylmethacrylates, acrylamide, methacrylamide, acrylic acid,
methacrylic acid, C1-C4-alkylacrylates,
C1-C4-alkylmethacrylates.
[0047] Especially, the polymeric surfactant A2 comprises or is
selected from homo- and copolymers of [0048] i) monomers M1, which
is 2-acrylamido-2-methylpropane sulfonic acid, [0049] ii) and
optionally one or more monoethylenically unsaturated comonomers M2
different from monomers M1, such as styrene, C1-C4-alkylacrylates,
C1-C4-alkylmethacrylates, acrylamide, methacrylamide, acrylic acid,
methacrylic acid, C1-C4-alkylacrylates,
C1-C4-alkylmethacrylates.
[0050] In these preferred, particular preferred or especially
preferred polymeric surfactants A.2, the amount of monomers M1 is
preferably at least 50% by weight, based on the total amount of
monomers forming the polymeric surfactant. Even more preferred are
polymeric surfactants A, which are homo- or copolymers of monomers
M1, wherein the amount of monomers M1 is at least 90% by weight,
based on the total amount of monomers forming the polymeric
surfactant. These polymers are known, e.g. from commercially
available under the tradenames Lupasol S and Lupasol PA 140.
[0051] In another particular group of embodiments, Microparticle
compositions according to the invention comprise surfactants of
group A3, polymeric surfactants A3 being arylsulfonic acid
formaldehyde condensates and arylsulfonic acid formaldehyde urea
condensates, in particular from naphthalene sulfonic acid
formaldehyde condensates. Examples or polymeric surfactants A3
include arylsulfonic acid formaldehyde condensates and arylsulfonic
acid formaldehyde urea condensates, such as naphthalene sulfonic
acid formaldehyde condensates, phenol sulfonic acid formaldehyde
condensates, cresol sulfonic acid formaldehyde condensates
etc.;
[0052] In one embodiment microparticle compositions according to
the invention comprise at least one surfactant A1 and no surfactant
A2 or A3.
[0053] In one embodiment microparticle compositions according to
the invention comprise at least one surfactant A1, at least one
surfactant A2 and no surfactant A3.
[0054] In one embodiment microparticle compositions according to
the invention comprise at least one surfactant A1, at least one
surfactant A3 and no surfactant A2.
[0055] In one embodiment microparticle compositions according to
the invention comprise at least one surfactant A1, at least one
surfactant A2 and at least one surfactant A3.
[0056] The amount of the anionic polymeric surfactants A1 to A3 in
the composition is preferably from 0.1 to 50% by weight, in
particular from 2 to 40% by weight and most preferred from 3 to 30%
by weight, based on the total amount of saflufenacil and aminoplast
polymer.
[0057] Polymeric surfactants A1 to A3 are herein also being
referred to polymeric surfactants A.
[0058] It was found beneficial, if the polymeric surfactants A1 to
A3 is combined with one or more further anionic surfactants B
different therefrom, which provide for the stabilization of an
aqueous formulation comprising the microparticles. Suitable anionic
surface-active compounds B are surfactants having one anionic
group, which is selected from phosphate or phosphonate groups and
sulfate or sulfonate groups, the latter compounds being preferred.
These surfactants B will usually be included into the microparticle
composition in the form of their salts, in particular the sodium,
potassium or ammonium salts. Examples of anionic surfactants B
include the salts of alkyl sulfonates, alkylsulfate, alkyl
phosphates, semi-esters of alkoxylated alkanols with sulfuric acid
or phosphoric acid, alkylarylsulfonates, alkylaryl phosphates,
semi-esters of alkoxylated alkylphenols with sulfuric acid or
phosphoric acid and semi-esters of alkoxylated mono-, di- or
tristyrylphenols with sulfuric acid or phosphoric acid. Amongst
these anionic surfactants B, those of the formula (I) are
preferred:
R--(O-A).sub.m-O--X (I)
wherein R is a hydrocarbon radical having from 8 to 40 carbon atoms
and preferably from 12 to 30 carbon atoms and optionally one oxygen
atom; A is independently from one another 1,2-ethylene,
1,2-propylene or 1,3-propylene, especially 1,2-ethylene; m is from
0 to 50, preferably from 0 to 30 and especially preferred from 0 to
20; and X is SO3M or PO3M2 with M being selected from H, alkaline
metal ions, such as K and Na, alkaline earth metal ions, such as
1/2 Ca and 1/2 Mg and ammonium.
[0059] Preferably, M is an alkaline metal ion and especially
sodium.
[0060] Examples of suitable hydrocarbon radicals R having from 8 to
40 carbon atoms are alkyl having from 8 to 40 and preferably from
12 to 30 carbon atoms, phenyl, which may be substituted with one or
two alkyl radicals having from 4 to 20 carbon atoms, phenyl, which
is substituted with a phenoxy radical, wherein phenyl and/or
phenoxy may contain an alkyl radical having from 4 to 20 carbon
atoms, tristyrylphenyl radical etc. In a preferred embodiment of
the present invention the radical R in formula I is a
tristyrylphenyl radical.
[0061] Preference is given to anionic surfactants B which are of
the formula (I), wherein R, m and X have the following
meanings:
R is alkyl having from 8 to 30, in particular from 10 to 20 carbon
atoms, m is 0, X is SO3M with m being selected from alkaline metal
ions, such as K and Na, alkaline earth metal ions, such as 1/2 Ca
and 1/2 Mg and ammonium. Preferably, M is an alkaline metal and
especially sodium.
[0062] Especially preferably, further anionic surfactant B is an
alkyl sulfate like lauryl sulfate, especially sodium lauryl
sulfate.
[0063] If present, the amount of anionic surfactant B, in
particular the surface-active compound of the formula (I), is
preferably from 0.1 to 10% by weight, in particular from 0.3 to 7%
by weight and most preferred from 0.5 to 5% by weight, based on the
total amount of saflufenacil and aminoplast polymer. If present,
the amount of anionic surfactant B, in particular the
surface-active compound of the formula (I), is preferably chosen
such that the weight ratio of anionic polymeric surfactant A to
anionic surfactant B is from 1:1 to 20:1 in particular from 2:1 to
10:1.
[0064] In one embodiment microparticle compositions according to
the invention comprise at least one surfactant A1 and no surfactant
A2 or A3 and anionic surfactant B is sodium lauryl sulfate.
[0065] In one embodiment microparticle compositions according to
the invention comprise at least one surfactant A1, at least one
surfactant A2 and no surfactant A3 and anionic surfactant B is
sodium lauryl sulfate.
[0066] In one embodiment microparticle compositions according to
the invention comprise at least one surfactant A1, at least one
surfactant A3 and no surfactant A2 and anionic surfactant B is
sodium lauryl sulfate.
[0067] In one embodiment microparticle compositions according to
the invention comprise at least one surfactant A1, at least one
surfactant A2 and at least one surfactant A3 and anionic surfactant
B is sodium lauryl sulfate.
[0068] The compositions according to the invention may also contain
a nonionic surface-active compound (nonionic surfactant). Preferred
nonionic surfactants include the neutral surface-active compounds
of the formula (II),
R'--(O--B)n--OH (II)
wherein R' is a hydrocarbon radical having from 8 to 40 and more
preferably from 12 to 30 carbon atoms and optionally one oxygen
atom, B is C2-C4-alkane-1,2-diyl, such as 1,2-ethylene,
1,2-propylene or 1,2-butylene or a combination thereof and more
preferred 1,2-ethylene or a combination thereof with 1,2-propylene,
and n is from 3 to 100, preferably from 4 to 50 and more preferred
from 5 to 40.
[0069] Preferred nonionic surfactants include block copolymers of
ethylene oxide (EO) and propylene oxide (PO). Such block copolymers
can for example have the structure R(EO)x-(PO)y-(EO)z, with R being
H or a C.sub.4 to C.sub.30 alkyl rest and x, y, z independently
being numbers from 2 to 100.
[0070] Examples of suitable hydrocarbon radials R' include the
radicals mentioned for R. In a preferred embodiment of the
invention the radical R' is a phenyl radical being substituted with
one C4-C18-alkyl group.
[0071] If present, the amount of nonionic surfactant, in particular
the surface-active compound of the formula (II), is preferably from
1 to 150 g/L, in particular from 2 to 60 g/L in the final
formulation. In one particular embodiment of the invention, the
composition does not contain nonionic surfactant or less than 1% by
weight of nonionic surfactant, in particular less than 0.5% by
weight of nonionic surfactant, based on the total amount of
saflufenacil and aminoplast polymer.
[0072] In particular groups of embodiments, the microparticle
composition is in the form of an aqueous suspension. Such a
suspension contains the microparticles of solid saflufenacil as a
disperse phase, and an aqueous medium as the continuous phase.
[0073] The aqueous suspension may be obtained by the process for
preparing the microparticle composition as described herein. It may
also be obtained by re-dispersing a solid microparticle composition
as described herein in an aqueous medium.
[0074] The term "aqueous medium" stands for the liquid phase of the
composition and comprises an aqueous solvent and optionally
compounds dissolved therein, e.g. surfactants as mentioned above,
and if present, conventional one or more conventional formulation
additives, such as thickeners or biocides. The aqueous solvent of
the aqueous suspension is either water or a mixture thereof with a
water-miscible organic solvent, such as C1-C4-alkanols, e.g.
methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol,
isobutanol, or tert. butanol, C2-05-alkanediols and
C3-C8-alkanetriols, preferably from the group consisting of
ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol and
1,4-butanediol. Generally, the amount of water in the aqueous
solvent is at least 50% by weight, in particular at least 80% by
weight or at least 90% by weight, based on the aqueous solvent. The
aqueous solvent may consist mainly of water, i.e. water makes up at
least 95% by weight of the total amount of solvent present in the
suspension. The aqueous solvent may also be a mixture of the
aforementioned water-miscible organic solvent and water. In the
latter case, the weight ratio of water to water-miscible organic
solvent in the aqueous solvent preferably is in the range of from
99:1 to 1:1; more preferably in the range of from 50:1 to 3:1; and
most preferably in the range of from 20:1 to 4:1. Expressed
differently the amount of organic solvent may be from 1 to 50% by
weight, more preferably from 2 to 25% by weight, and most
preferably from 5 to 20% by weight, based on the total weight of
the aqueous solvent.
[0075] The aqueous suspension will usually contain the
microparticles in an amount of at least 5% by weight and the amount
may be as high as 50% by weight or even higher, in each case based
on the total weight of the aqueous suspension and calculated as the
total amount of aminoplast-polymer and saflufenacil. Frequently,
the aqueous suspension will contain the microparticles in an amount
from 10 to 45% by weight, in particular from 20 to 40% by weight,
in each case based on the total weight of the aqueous suspension
and calculated as the total amount of aminoplast-polymer and
saflufenacil. The concentration of saflufenacil in the aqueous
suspension will frequently be in the range from 5 to 40% by weight,
in particular from 15 to 30% by weight, based on the total weight
of the aqueous suspension.
[0076] If present, the concentration of the polymeric anionic
surfactant A in the aqueous suspension will frequently be in the
range from 0.1 to 15% by weight, in particular from 0.2 to 6% by
weight, based on the total weight of the aqueous suspension of the
microparticles.
[0077] If present, the concentration of the anionic surfactant B in
the aqueous suspension will frequently be in the range from 0.1 to
15% by weight, in particular from 0.2 to 6% by weight, based on the
total weight of the aqueous suspension of the microparticles.
[0078] The aqueous compositions according to the invention may also
comprise customary formulation auxiliaries, such as
viscosity-modifying additives (thickeners), antifoam agents,
preservatives, buffers, inorganic dispersants, etc., which are
usually employed in aqueous formulations of herbicides. Such
auxiliaries may be incorporated into the aqueous suspension after
step iii) of the preparation process described herein has been
carried out. The amount of additives will generally not exceed 10%
by weight, in particular 5% by weight of the total weight of the
aqueous suspension. Suitable inorganic dispersants, also termed
anticaking agents, for preventing agglutination of the
microparticles, are silica (such as, for example Sipernat.RTM. 22
from Degussa), alumina, calcium carbonate and the like. In the
context of the present invention silica is a preferred inorganic
dispersant. The concentration of inorganic dispersants in the final
suspension will generally not exceed 2% by weight, based on the
total weight of the final suspension, and, if present, it is
preferably in the range from 0.01 to 2% by weight, in particular
from 0.02 to 1.5% by weight and especially from 0.1 to 1% by
weight, based on the total weight of the final formulation.
[0079] Suitable thickeners are compounds which affect the flow
behavior of the suspension concentrate and may assist in
stabilizing the aqueous suspension of the microparticles against
caking. Mention may be made, in this connection, for example, of
commercial thickeners based on polysaccharides, such as
methylcellulose, carboxymethylcellulose, hydroxypropyl cellulose
(Klucel.RTM. grades), Xanthan Gum (commercially available e.g. as
Kelzan.RTM. grades from Kelco or Rhodopol.RTM. grades from Rhodia),
synthetic polymers, such as acrylic acid polymers (Carbopol.RTM.
grades), polyvinyl alcohol (e.g. Mowiol.RTM. and Poval.RTM. grades
from Kuraray) or polyvinyl pyrrolones, silicic acid or
phyllosilicates, such as montmorillonite and bentonites, which may
be hydrophobized, (commercially available as Attaclay.RTM. grades
and Attaflow.RTM. grades from BASF SE; or as Veegum.RTM. grades and
Van Gel.RTM. grades from R.T. Vanderbilt). In the context of the
present invention, Xanthan Gum is a preferred thickener. The
concentration of thickeners in the aqueous suspension will
generally not exceed 2% by weight, based on the total weight of the
aqueous suspension, and is preferably in the range from 0.01 to 2%
by weight, in particular from 0.02 to 1.5% by weight and especially
from 0.1 to 1% by weight, based on the total weight of the aqueous
suspension or the final formulation, respectively.
[0080] Antifoam agents suitable for the compositions according to
the invention are, for example, silicone emulsions (such as, for
example, Silicone SRE-PFL from Wacker or Rhodorsil.RTM. from
Bluestar Silicones), polysiloxanes and modified polysiloxanes
including polysiloxane blockpolymers such as FoamStar.RTM. SI and
FoamStar.RTM. ST products of BASF SE, long-chain alcohols, fatty
acids, organofluorine compounds and mixtures thereof.
[0081] Suitable preservatives to prevent microbial spoiling of the
compositions of the invention include formaldehyde, alkyl esters of
p-hydroxybenzoic acid, sodium benzoate,
2-bromo-2-nitropropane-1,3-diol, o-phenylphenol, thiazolinones,
such as benzisothiazolinone, 5-chloro-2-methyl-4-isothiazolinone,
pentachlorophenol, 2,4-dichlorobenzyl alcohol and mixtures thereof.
Commercially available preservatives that are based on
isothiazolinones are for example marketed under the trademarks
Proxel.RTM. (Arch Chemical), Acticide.RTM. MBS (Thor Chemie) and
Kathon.RTM. MK (Rohm & Haas).
[0082] If appropriate, the compositions according to the invention,
in particular the aqueous suspensions, may comprise buffers to
regulate the pH. Examples of buffers are alkali metal salts of weak
inorganic or organic acids such as, for example, phosphoric acid,
boric acid, acetic acid, propionic acid, citric acid, fumaric acid,
tartaric acid, oxalic acid and succinic acid.
[0083] In addition, the compositions according to the invention, in
particular the aqueous suspensions, can be formulated with
conventional binders, for example aqueous polymer dispersions,
water-soluble resins, for example water-soluble alkyd resins, or
waxes.
[0084] The compositions of the invention may also contain one or
more adjuvants. Suitable adjuvants are known to skilled persons and
include surfactants, crop oil concentrates, spreader-stickers,
wetting agents, and penetrants. In other particular groups of
embodiments, the microparticle composition is in the form of solid
composition. Such a solid composition contains the microparticles
of solid saflufenacil, optionally one or more surfactants, in
particular the polymeric surfactant A and optionally the anionic
surfactant B, and optionally an inert solid carrier material.
[0085] The solid compositions may e.g. be redispersible powders,
water-dispersible granules wettable powders and the like.
[0086] Solid carriers include e.g. mineral earths, such as silicas,
silica gels, silicates, talc, kaolin, lime stone, lime, chalk,
bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,
magnesium sulfate, magnesium oxide, ground synthetic materials,
fertilizers such as ammonium sulfate, ammonium phosphate, ammonium
nitrate, ureas, and products of vegetable origin, such as cereal
meal, tree bark meal, wood meal and nutshell meal, cellulose
powders, or other solid carriers.
[0087] The solid compositions according to the invention may also
comprise customary formulation auxiliaries, such as antifoam
agents, preservatives, buffers, inorganic dispersants, etc., which
are usually employed in solid formulations of herbicides. Such
auxiliaries may be incorporated into the solid formulation at any
conventional stage of their preparation process. The amount of
additives will generally not exceed 10% by weight, in particular 5%
by weight of the total weight of the solid composition.
[0088] The solid composition may be obtained from an aqueous
suspension which is primarily formed in the process for preparing
the microparticle composition as described herein by removing the
aqueous phase from the aqueous suspension. Removal of the aqueous
phase can be achieved by either separating the aqueous phase from
the solid microparticles, e.g. by centrifugation or filtration.
Preferably, the aqueous phase is removed by an evaporation process,
such as spray drying or freeze drying.
[0089] As outlined above, the process for producing the composition
comprises a first step, where an aqueous suspension of saflufenacil
particles is provided. For this, solid saflufenacil is suspended in
an aqueous solvent, in particular in water. The aqueous solvent may
contain one or more surfactants, in particular at least one
polymeric surfactant A1, which is assumed to act as a protective
colloid, and optionally one or more anionic surfactants B.
[0090] Preferably, the particle size of the saflufenacil particles
in the aqueous suspension prior to encapsulation is less than 45
.mu.m, in particular it will not exceed 40 .mu.m, preferably not
exceed 30 .mu.m and in particular not exceed 25 .mu.m. The particle
size given is the so called d90-value. Preferably the active
substance particles have an average particle diameter, herein also
termed d50-value, ranging from 0.5 to 25 .mu.m, in particular from
1 to 20 .mu.m, especially from 1.5 to 15 .mu.m. The d50-value is
defined as the value that is above the diameters of 50% by weight
of the particles and below the diameters of 50% by weight of the
particles. The d10-value is preferably at least 0.5 .mu.m and may
e.g. be in the range from 0.5 .mu.m 10 .mu.m, in particular from 1
to 5 .mu.m. The d90 value as well as the d50 value can be
calculated from the particle size distribution of the saflufenacil
particles which can be determined by conventional methods such as
dynamic or static light-scattering at 25.degree. C. and a
concentration in the range of 0.1 to 1% by weight.
[0091] It has been found beneficial, if the polycondensation is
initiated or effected in the presence of at least one anionic
polymeric surfactant A2. Polymeric surfactant A2 will frequently be
in the range from 0.1 to 10% by weight, in particular from 1 to 6%
by weight, based on the total weight of the aqueous suspension.
[0092] It has been found beneficial, if the aqueous suspension of
step i) also contains at least one anionic surfactant B, in
particular an anionic surfactant which comprises or is selected
from the surfactants of the formula (I). If present, the
concentration of the anionic surfactant B in the aqueous suspension
of step i) will frequently be in the range from 0.01 to 2% by
weight, in particular from 0.1 to 1% by weight, based on the total
weight of the aqueous suspension.
[0093] The aqueous suspension of the saflufenacil particles can be
provided by analogy to known methods of preparing aqueous
suspensions of saflufenacil, e.g. as described in WO
2011/023759.
[0094] In one embodiment, step i) comprises a step i.a) and a step
i.b). In step i.a) solid saflufenacil, in particular a crystalline
form of saflufenacil, such as saflufenacil anhydrate or one of the
hydrate forms, and the aqueous solvent and optionally at least a
part of the surfactant are mixed in any conventional mixing device
which is capable of providing sufficient shear to form the desired
suspension. Suitable mixing devices include in particular high
shear mixers, such as Ultra-Turrax apparatus, static mixers, e.g.
systems having mixing nozzles, agitator bead mills, colloid mills,
cone mills and other homogenizers. In general, the sequence in
which the individual components are combined is not critical. It
may be advantageous to carry step i.a) out by firstly mixing the
aqueous solvent and at least a part of the surfactant, e.g. the
surfactant of group A
and optionally the surfactant B, until a homogenous mixture is
obtained, and then adding the solid saflufenacil with shear to said
homogenous mixture. The mixture obtained from step i.a), i.e. a
coarse suspension of saflufenacil in the aqueous solvent, is then
subjected in step i.b) to suitable means for reducing the particle
size of the saflufenacil particles present in the mixture typically
to below 40 .mu.m, preferably to below 30 .mu.m and in particular
to below 20 .mu.m (d90-value), e.g. to a particle size (d90) in the
range from 0.5 to 15 .mu.m. Step i.b) may be carried out by any
physical attrition method, such as grinding, crushing or milling,
in particular by wet grinding or wet milling, including e.g. bead
milling, hammer milling, jet milling, air classifying milling, pin
milling, cryogenic grinding processes and the like. Steps i.a) and
i.b) are usually performed subsequently. However, it is also
possible to perform these steps together.
[0095] In another embodiment of the invention, step i) comprises
providing saflufenacil in the form of a powder, wherein the d90
value of the powder particles is below 40 .mu.m and in particular
at most 30 .mu.m or at most 20 .mu.m, e.g. the particle size (d90)
is in the range from 1 to <40 .mu.m, in particular 1 to 30 .mu.m
or 1 to 20 .mu.m. The powder is usually prepared by comminuting the
solid saflufenacil, e.g. the anhydrate or the crystalline hydrate,
by a conventional dry milling technique, such as air milling, to a
powder having the desired particle size. The thus obtained powder
is then be suspended in the aqueous solvent or in an aqueous
solution of the surfactant of group A and optionally the surfactant
B.
[0096] In one embodiment, polymeric surfactants A2 are added to the
suspension of the saflufenacil provided in step i) before starting
or initiating or effecting the polycondensation, in particular
before adding the aminoplast pre-condensate thereto. In particular,
it may be beneficial to keep the aqueous suspension of
saflufenacil, which contains the polymeric surfactant A2, for some
time, e.g. for 10 to 180 minutes, before starting the
polycondensation, while polymeric surfactant A1 is only added after
step i). In step ii), an aminoplast pre-condensate is added to the
aqueous suspension of step i), which, upon curing in step iii),
forms the solid, water-insoluble aminoplast polymer, which embeds
or surrounds the solid saflufenacil particles, because the
polycondensation preferentially occurs on the surface of the solid
saflufenacil particles.
[0097] The amount of aminoplast pre-condensate added in step ii) is
chosen such that the desired amount of aminoplast polymer in the
final microparticle composition is achieved. In fact, the amount
added corresponds to the amount of aminoplast resin in the
microparticles, taking into account that the mass is reduced by the
amount of water which is formed during the polycondensation, and is
usually in the range 0.5 to 40% by weight, in particular from 1 to
35% by weight and especially from 5 to 25% by weight, based on
saflufenacil and calculated as organic matter.
[0098] Suitable pre-condensates, which can be added in step ii)
include pre-condensates of melamine and formaldehyde, including
wholly or partially etherified melamine formaldehyde
pre-condensates, urea-formaldehyde pre-condensates, thiourea
formaldehyde pre-condensates, pre-condensates of melamine, urea and
formaldehyde (MUF resins), including mixtures of wholly or
partially etherified melamine formaldehyde precondensates and
urea-formaldehyde pre-condensates, precondensates of urea and
glutaraldehyde, pre-condensates of benzoguanamine and formaldehyde,
mixtures of dicyandiamide and formaldehyde and urea-glyoxal
polycondensates. Suitable aminoplast pre-condensates for
microencapsulation are known and can be found, inter alia, in
Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd edition, Vol.
2, pp. 440-469, the prior art cited in the introductory part, U.S.
Pat. No. 4,918,317, EP 26914, EP 218887, EP 319337, EP 383,337, EP
415273, DE 19833347, DE 19835114 and WO 01/51197. Suitable
pre-condensates are commercially available, e. g. Cymel types, such
as but not limited to Cymel.RTM. 303, 327, 328 or 385 (etherified
melamine formaldehyde resins of Cytec), Maprenal.RTM. types, such
as but not limited to Maprenal.RTM. MF 900w/95, MF 915/75IB, MF
920/75WA, MF 921w/85WA, (etherified melamine formaldehyde resins of
Ineos), Kauramin.RTM. types of BASF SE, such as but not limited to
Kauramin.RTM. 783, Kauramin.RTM. 792 or Kauramin.RTM. 753 (melamine
formaldehyde resins), Kauramin.RTM. 620 or Kauramin.RTM. 621
(melamine urea formaldehyde resins), Kaurit.RTM. types of BASF SE,
such as but not limited to Kaurit.RTM. 210, 216, 217 or 220 (urea
formaldehyde resins), Luracoll.RTM. types such as Luracoll.RTM. SD
(etherified melamine formaldehyde resins), Luwipal.RTM. types such
as but not limited to Luwipal.RTM. 063, Luwipal.RTM. 069
(etherified melamine formaldehyde resins), or Plastopal.RTM. types
such as but not limited to Plastopal.RTM. BTM, Plastopal.RTM. BTW
(etherified urea formaldehyde resins).
[0099] In suitable urea-formaldehyde or thiourea-formaldehyde
pre-condensates, the molar ratios of urea or thiourea to
formaldehyde are generally in the range from 1:0.8 to 1:4, in
particular from 1:1.5 to 1:4, especially from 1:2 to 1:3.5.
[0100] In suitable melamine-formaldehyde or
melamine-(thio)urea-formaldehyde pre condensates, the molar ratios
of melamine to formaldehyde are generally in the range from 1:1.5
to 1:10, in particular from 1:3 to 1:8 preferably 1:4 to 1:6.
[0101] In suitable melamine-formaldehyde or
melamine-(thio)urea-formaldehyde precondensates, the molar ratios
of melamine+urea or thiourea to formaldehyde are generally in the
range from 1:0.8 to 1:9, in particular from 1:2 to 1:8 preferably
1:3 to 1:6. The molar ratio of urea or thiourea to melamine is
usually in the range from 5:1 to 1:50 and in particular from 30:1
to 1:30.
[0102] The pre-condensates may be used in the form of etherified
pre-condensates of amino compound and aldehyde. In these etherified
pre-condensates the methylol groups formed by the reaction of the
amino groups with formaldehyde with an alkanol or an alkane diol,
in particular with a C1-C4-alkanol, such as methanol, ethanol,
n-propanol or n-butanol, in particular methanol, or a
C2-C4-alkandiol, such as ethylene glycol. The degree of
etherification of these resins can be adjusted by the molar ratio
of amino groups to alkanol which is typically in the range from
10:1 to 1:10, preferably in the range from 2:1 to 1:5.
[0103] The pre-condensates are most preferably selected from the
group consisting of melamine-formaldehyde resins, including wholly
or partially etherified melamine formaldehyde pre-condensates, and
urea-formaldehyde pre-condensates and mixtures thereof. Especially,
the pre-condensate is a wholly or partially etherified melamine
formaldehyde condensate, which may contain small amounts, e.g. 1 to
20 mol.-%, based on melamine, of urea.
[0104] Addition of the pre-condensate to the aqueous suspension is
normally achieved by adding the pre-condensate in the form of an
aqueous or alcoholic solution of the pre-condensate to the aqueous
suspension or by mixing suitable amounts of the dissolved
pre-condensate. Preferably, suitable mixing devices, such as
stirrers or inline-mixers are used in order to achieve a uniform
distribution of the pre-condensate in the aqueous suspension. It
may be beneficial to add the pre-condensate, preferably in the form
of a solution, to the aqueous suspension of saflufenacil with
stirring. Preferably, the addition of the pre-condensate is
performed under conditions, where the polycondensation reaction is
slow or does not occur, e.g. where either the pH of the aqueous
suspension at least pH 6, e.g. in the range form pH 6 to pH 10, or
where the temperature does not exceed 30.degree. C. or both.
[0105] The polycondensation of the aminoplast pre-condensate can be
effected or initiated in a well-known manner, e.g. by heating the
aqueous suspension to a certain reaction temperature, at a pH,
where the polycondensation at the reaction temperature occurs.
During the polycondensation, the aminoplast pre-condensate is
converted into a water-insoluble aminoplast resin, which
precipitates from the aqueous phase and deposits preferably on the
surface of the solid saflufenacil particles, thereby embedding or
surrounding the solid saflufenacil particles. Thereby, it is
possible to a achieve an efficient encapsulation even with small
amounts of the aminoplast pre-condensate. Preferably, the
polycondensation of the aminoplast is performed at pH of less than
pH 6, in particular at a pH of at most pH 5, e.g. in the range of
pH 0 to 6, more particularly in the range from pH 1 to 5 or in the
range from pH 2 to 4.
[0106] The pH of the aqueous suspension is usually adjusted by
addition of suitable amounts of an organic or inorganic acid, such
as sulfuric acid, hydrochloric acid, phosphoric acid, a carboxylic
acid including alkanoic acids, alkane dioic acids or
hydroxycarboxylic acids, such as formic acid, acetic acid,
propionic acid, oxalic acid, malic acid or citric acid, and alkyl
or arylsulfonic acids, such as methane sulfonic acid or toluene
sulfonic acid. It is preferred, if at least a portion, in
particular the majority of the acid is present in the aqueous
suspension, before the aqueous suspension is heated to the reaction
temperature.
[0107] Preferably, the polycondensation of the aminoplast
pre-condensate is performed at elevated temperature, in particular
at a temperature of at least 30.degree. C., in particular at least
40.degree. C. or at least 50.degree. C., e.g. at a temperature in
the range of 30 to 100.degree. C., in particular in the range of 40
to 95.degree. C. or in the range of 50 to 90.degree. C. It may be
possible to effect the start of the polycondensation of the
aminoplast at a comparatively low temperature, e.g. a temperature
in the range of 30 to 65.degree. C. or 35 to 60.degree. C. and then
complete the polycondensation reaction at a higher temperature of
e.g. 50 to 100.degree. C. or 60 to 90.degree. C. The time for
completing the polycondensation may vary, depending on the
reactivity of the pre-condensate, the temperature and the pH of the
aqueous suspension and may take from 1 h to 24 h, in particular
from 2 to 12 h. Preferably, the polycondensation reaction is at
least partly performed at temperatures of at least 50.degree. C.,
in particular at least 60.degree. C., e.g. for 1 to 8 h at a
temperature in the range from 50 to 100.degree. C., in particular
60 to 90.degree. C.
[0108] The thus obtained aqueous suspension of the saflufenacil
microparticles may be neutralized by the addition of a base.
Preferably, the pH of the suspension is adjusted to a pH of at
least 6, e.g. a pH in the range of pH 6 to 10, in particular in the
range of pH 6.5 to 9.0. In one preferred embodiment the base used
is ammonia, especially aqueous ammonia.
[0109] From the thus obtained aqueous suspension the microparticles
can be isolated, e.g. by filtration or centrifugation, or the
aqueous suspension may be spray-dried, granulated or freeze-dried,
to obtain a solid composition in the form of a powder or granules.
The solid composition may be re-dispersed or formulated by using
formulation auxiliaries as described above.
[0110] The aqueous suspension may also be used as such or
formulated as a liquid formulation, e.g. as a suspension, by using
suitable formulation auxiliaries as described above, e.g. such as
thickeners, anionic surfactants B, non-ionic surfactants and/or
biocides.
[0111] The invention also relates to uses of the microparticle
composition of the invention for protecting crop plants and to
methods of controlling undesired vegetation, which comprise
applying the formulations, in diluted or undiluted form, to plants,
their environment and/or seeds.
[0112] The compositions of the invention provide for a very good
control of vegetation in noncrop areas, especially at high
application rates. However, generally no higher application rates
are required in comparison with conventional formulations of
non-encapsulated saflufenacil for achieving similar control.
[0113] In crops such as soybean, cotton, oilseed rape, flax,
lentils, rice, sugar beet, sunflower, tobacco and cereals, such as,
for example maize or wheat, the compositions of the invention are
active against broad-leaved weeds and grass weeds and provide for
less damage to the crop plants in comparison with conventional
formulations of non-encapsulated saflufenacil. This effect is
particularly observed at low application rates.
[0114] Furthermore, the compositions of the invention provide for
long lasting residual activity, which exceeds the residual activity
of conventional formulations of non-encapsulated saflufenacil.
[0115] The compositions according to the invention have an
outstanding herbicidal activity against undesired vegetation, in
particular against a broad spectrum of economically important
harmful monocotyledonous and dicotyledonous weeds.
[0116] Mentioned below are some representatives of monocotyledonous
and dicotyledonous weeds, which can be controlled by compositions
according to the invention, without the enumeration being a
restriction to certain species.
[0117] In one embodiment, compositions according to the invention
are used to control monocotyledonous weeds.
[0118] Examples of monocotyledonous weeds on which compositions of
the invention act efficiently are selected from the genera Hordeum
spp., Echinochloa spp., Poa spp., Bromus spp., Digitaria spp.,
Eriochloa spp., Setaria spp., Pennisetum spp., Eleusine spp.,
Eragrostis spp., Panicum spp., Lolium spp., Brachiaria spp.,
Leptochloa spp., Avena spp., Cyperus spp., Axonopris spp., Sorghum
spp., and Melinus spp..
[0119] Preferred examples of monocotyledonous weeds on which
compositions of the invention act efficiently are selected from the
species Hordeum murinum, Echinochloa crus-galli, Poa annus, Bromus
rubens L., Bromus rigidus, Bromus secalinus L., Digitaria
sanguinalis, Digitaria insularis, Eriochloa gracilis, Setaria
faberi, Setaria viridis, Pennisetum glaucum, Eleusine indica,
Eragrostis pectinacea, Panicum miliaceum, Lolium multiflorum,
Brachiaria platyphylla, Leptochloa fusca, Avena fatua, Cyperus
compressus, Cyperus esculentes, Axonopris offinis, Sorghum
halapense, and Melinus repens.
[0120] Especially preferred examples of monocotyledonous weeds on
which compositions of the invention act efficiently are selected
from the species Echinochloa spp., Digitaria spp., Setaria spp.,
Eleusine spp. and Brachiarium spp.
[0121] In one embodiment compositions of the invention are used to
control dicotyledonous weeds.
[0122] Examples of dicotyledonous weeds on which compositions of
the invention act efficiently are selected from the genera
Amaranthus spp., Erigeron spp., Conyza spp., Polygonum spp.,
Medicago spp., Mollugo spp., Cyclospermum spp., Stellaria spp.,
Gnaphalium spp., Taraxacum spp., Oenothera spp., Amsinckia spp.,
Erodium spp., Erigeron spp., Senecio spp., Lamium spp., Kochia
spp., Chenopodium spp., Lactuca spp., Malva spp., Ipomoea spp.,
Brassica spp., Sinapis spp., Urtica spp., Sida spp, Portulaca spp.,
Richardia spp., Ambrosia spp., Calandrinia spp., Sisymbrium spp.,
Sesbania spp., Capsella spp., Sonchus spp., Euphorbia spp.,
Helianthus spp., Coronopus spp., Salsola spp., Abutilon spp., Vicia
spp., Epilobium spp., Cardamine spp., Picris spp., Trifolium spp.,
Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp.,
Oxalis spp., Metricaria spp., Plantago spp., Tribulus spp.,
Cenchrus spp. Bidens spp., Veronica spp., and Hypochaeris spp..
[0123] Preferred examples of dicotyledonous weeds on compositions
of the invention act efficiently are selected from the species
Amaranthus spinosus, Polygonum convolvulus, Medicago polymorphs,
Mollugo verticillata, Cyclospermum leptophyllum, Stellaria media,
Gnaphalium purpureum, Taraxacum officinale, Oenothera laciniata,
Amsinckia intermedia, Erodium cicutarium, Erodium moschatum,
Erigeron bonariensis (Conyza bonariensis), Senecio vulgaris, Lamium
amplexicaule, Erigeron canadensis, Polygonum aviculare, Kochia
scoparia, Chenopodium album, Lactuca serriola, Malva parviflora,
Malva neglecta, Ipomoea hederacea, Ipomoea lacunose, Brassica
nigra, Sinapis arvensis, Urtica dioica, Amaranthus blitoides,
Amaranthus retroflexus, Amaranthus hybridus, Amaranthus lividus,
Sida spinosa, Portulaca oleracea, Richardia scabra, Ambrosia
artemisiifolia, Calandrinia caulescens, Sisymbrium irio, Sesbania
exaltata, Capsella bursa pastoris, Sonchus oleraceus, Euphorbia
maculate, Helianthus annuus, Coronopus didymus, Salsola tragus,
Abutilon theophrasti, Vicia benghalensis L., Epilobium paniculatum,
Cardamine spp, Picris echioides, Trifolium spp., Galinsoga spp.,
Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp.,
Metricaria matriccarioides, Plantago spp., Tribulus terrestris,
Salsola kali, Cenchrus spp., Bidens bipinnata, Veronica spp., and
Hypochaeris radicata.
[0124] Especially preferred examples of dicotyledonous weeds on
which compositions of the invention act efficiently are selected
from the species Amaranthus spp., Erigeron spp., Conyza spp.,
Kochia spp. and Abutilon spp.
[0125] Depending on the application method in question, the
formulations of the invention can additionally be employed in a
further number of crop plants to remove undesired plants. Crops
which are suitable are, for example, the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus
officinalis, Avena sativa, Beta vulgaris spec. altissima, Beta
vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var.
napobrassica, Brassica rapa var. silvestris, Brassica oleracea,
Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya
illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica
(Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon
dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine
max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum,
Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis,
Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia,
Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum,
Malus spec., Manihot esculenta, Medicago sativa, Musa spec.,
Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa,
Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec.,
Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus
communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and
Prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum
officinarum, Secale cereale, Sinapis alba, Solanum tuberosum,
Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense,
Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis
vinifera and Zea mays.
[0126] Preferred crops are Arachis hypogaea, Beta vulgaris spec.
altissima, Brassica napus var. napus, Brassica oleracea, Citrus
limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea
liberica), Cynodon dactylon, Glycine max, Gossypium hirsutum,
(Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium),
Helianthus annuus, Hordeum vulgare, Juglans regia, Lens culinaris,
Linum usitatissimum, Lycopersicon lycopersicum, Malus spec.,
Medicago sativa, Nicotiana tabacum (N.rustica), Olea europaea,
Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Pistacia vera,
Pisum sativum, Prunus dulcis, Saccharum officinarum, Secale
cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare),
Triticale, Triticum aestivum, Triticum durum, Vicia faba, Vitis
vinifera and Zea mays.
[0127] Especially preferred crops are crops of cereals, corn,
soybeans, rice, oilseed rape, cotton, potatoes, peanuts or
permanent crops.
[0128] In addition, the compositions of the invention can also be
used in crops which tolerate the effect of herbicides as the result
of breeding, including genetic engineering methods.
[0129] Furthermore, the compositions of the invention can also be
used in crops which tolerate attack by insects or fungi as the
result of breeding, including genetic engineering methods.
[0130] Compositions of the invention can also be used in crops
which have been modified by mutagenesis or genetic engineering in
order to provide a new trait to a plant or to modify an already
present trait.
[0131] The term "crops" as used herein includes also (crop) plants
which have been modified by mutagenesis or genetic engineering in
order to provide a new trait to a plant or to modify an already
present trait.
[0132] Mutagenesis includes techniques of random mutagenesis using
X-rays or mutagenic chemicals, but also techniques of targeted
mutagenesis, in order to create mutations at a specific locus of a
plant genome. Targeted mutagenesis techniques frequently use
oligonucleotides or proteins like CRISPR/Cas, zinc-finger
nucleases, TALENs or meganucleases to achieve the targeting
effect.
[0133] Genetic engineering usually uses recombinant DNA techniques
to create modifications in a plant genome which under natural
circumstances cannot readily be obtained by cross breeding,
mutagenesis or natural recombination. Typically, one or more genes
are integrated into the genome of a plant in order to add a trait
or improve a trait. These integrated genes are also referred to as
transgenes in the art, while plant comprising such transgenes are
referred to as transgenic plants. The process of plant
transformation usually produces several transformation events,
which differ in the genomic locus in which a transgene has been
integrated. Plants comprising a specific transgene on a specific
genomic locus are usually described as comprising a specific
"event", which is referred to by a specific event name. Traits
which have been introduced in plants or have been modified include
in particular herbicide tolerance, insect resistance, increased
yield and tolerance to abiotic conditions, like drought.
[0134] Herbicide tolerance has been created by using mutagenesis as
well as using genetic engineering. Plants which have been rendered
tolerant to acetolactate synthase (ALS) inhibitor herbicides by
conventional methods of mutagenesis and breeding comprise plant
varieties commercially available under the name Clearfield.RTM..
However, most of the herbicide tolerance traits have been created
via the use of transgenes. Herbicide tolerance has been created to
glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like
bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor
herbicides and 4-hydroxyphenylpyruvate dioxygenase (HPPD)
inhibitors, like isoxaflutole and mesotrione.
[0135] Transgenes which have been used to provide herbicide
tolerance traits comprise: for tolerance to glyphosate: cp4 epsps,
epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for
tolerance to glufosinate: pat and bar, for tolerance to 2,4-D:
aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to
oxynil herbicies: bxn, for tolerance to sulfonylurea herbicides:
zm-hra, csrl-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor
herbicides: csrl-2, for tolerance to HPPD inhibitor herbicides:
hppdPF, W336 and avhppd-03.
[0136] Transgenic corn events comprising herbicide tolerance genes
are for example, but not excluding others, DAS40278, MON801,
MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427,
MON88017, MON89034, NK603, GA21, MZHGOJG, HCEM485, VCO-01981-5,
676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351,
DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.
[0137] Transgenic soybean events comprising herbicide tolerance
genes are for example, but not excluding others, GTS 40-3-2,
MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12,
A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4,
DAS-81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
[0138] Transgenic cotton events comprising herbicide tolerance
genes are for example, but not excluding others, 19-51a, 31707,
42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215,
BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119,
GHB614, LLCotton25, T303-3 and T304-40.
[0139] Transgenic canola events comprising herbicide tolerance
genes are for example, but not excluding others, MON88302, HCR-1,
HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2
and RF3.
[0140] Insect resistance has mainly been created by transferring
bacterial genes for insecticidal proteins to plants. Transgenes
which have most frequently been used are toxin genes of Bacillus
spec. and synthetic variants thereof, like crylA, crylAb,
crylAb-Ac, crylAc, crylA.105, crylF, crylFa2, cry2Ab2, cry2Ae,
mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a),
vip3Aa20. However, also genes of plant origin have been transferred
to other plants. In particular genes coding for protease
inhibitors, like CpTI and pinll. A further approach uses transgenes
in order to produce double stranded RNA in plants to target and
downregulate insect genes. An example for such a transgene is
dvsnf7.
[0141] Transgenic corn events comprising genes for insecticidal
proteins or double stranded RNA are for example, but not excluding
others, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863,
MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507,
TC6275, CBH-351, MIR162, DBT418 and MZIR098.
[0142] Transgenic soybean events comprising genes for insecticidal
proteins are for example, but not excluding others, MON87701,
MON87751 and DAS-81419.
[0143] Transgenic cotton events comprising genes for insecticidal
proteins are for example, but not excluding others, SGK321, MON531,
MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317,
BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM CrylA, GK12,
MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.
[0144] Increased yield has been created by increasing ear biomass
using the transgene athb17, being present in corn event MON87403,
or by enhancing photosynthesis using the transgene bbx32, being
present in the soybean event MON87712.
[0145] Crops comprising a modified oil content have been created by
using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and
fatb1-A. Soybean events comprising at least one of these genes are:
260-05, MON87705 and MON87769.
[0146] Tolerance to abiotic conditions, in particular to tolerance
to drought, has been created by using the transgene cspB, comprised
by the corn event MON87460 and by using the transgene Hahb-4,
comprised by soybean event IND-OO41O-5.
[0147] Traits are frequently combined by combining genes in a
transformation event or by combining different events during the
breeding process. Preferred combination of traits are herbicide
tolerance to different groups of herbicides, insect tolerance to
different kind of insects, in particular tolerance to lepidopteran
and coleopteran insects, herbicide tolerance with one or several
types of insect resistance, herbicide tolerance with increased
yield as well as a combination of herbicide tolerance and tolerance
to abiotic conditions.
[0148] Plants comprising singular or stacked traits as well as the
genes and events providing these traits are well known in the art.
For example, detailed information as to the mutagenized or
integrated genes and the respective events are available from
websites of the organizations "International Service for the
Acquisition of Agri-biotech Applications (ISAAA)"
(http://www.isaaa.org/gmapprovaldatabase) and the "Center for
Environmental Risk Assessment (CERA)"
(http://cera-gmc.org/GMCropDatabase), as well as in patent
applications, like EP3028573 and WO2017/011288.
[0149] The use of the compounds of formula (I) or formulations or
combinations comprising them according to the invention on crops
may result in effects which are specific to a crop comprising a
certain gene or event. These effects might involve changes in
growth behavior or changed resistance to biotic or abiotic stress
factors. Such effects may in particular comprise enhanced yield,
enhanced resistance or tolerance to insects, nematodes, fungal,
bacterial, mycoplasma, viral or viroid pathogens as well as early
vigour, early or delayed ripening, cold or heat tolerance as well
as changed amino acid or fatty acid spectrum or content.
[0150] Furthermore, plants are also covered that contain by the use
of recombinant DNA techniques a modified amount of ingredients or
new ingredients, specifically to improve raw material production,
e.g., potatoes that produce increased amounts of amylopectin (e.g.
Amflora.RTM. potato, BASF SE, Germany).
[0151] Furthermore, it has been found that compositions of the
invention are also suitable for the defoliation and/or desiccation
of plant parts of crops such as cotton, potato, oilseed rape,
sunflower, soybean or field beans, in particular cotton. In this
regard, formulations and/or combinations for the desiccation and/or
defoliation of crops, processes for preparing these formulations
and/or combinations and methods for desiccating and/or defoliating
plants using compositions of the invention have been found. As
desiccants, compositions of the invention are particularly suitable
for desiccating the above-ground parts of crop plants such as
potato, oilseed rape, sunflower and soybean, but also cereals. This
makes possible the fully mechanical harvesting of these important
crop plants.
[0152] Also of economic interest is to facilitate harvesting, which
is made possible by concentrating within a certain period of time
the dehiscence, or reduction of adhesion to the tree, in citrus
fruit, olives and other species and varieties of pernicious fruit,
stone fruit and nuts. The same mechanism, i.e. the promotion of the
development of abscission tissue between fruit part or leaf part
and shoot part of the plants is also essential for the controlled
defoliation of useful plants, in particular cotton.
[0153] Moreover, a shortening of the time interval in which the
individual cotton plants mature leads to an increased fiber quality
after harvesting.
[0154] Moreover, it has been found that the compositions of the
invention are also suitable for the control of conifers, in
particular of conifer seedlings which grow naturally, and
specifically for the control of pine seedlings which grow
naturally.
[0155] In general, the compositions of the invention as described
herein are useful for combating undesired vegetation. For this
purpose, the compositions may be applied as such or are preferably
applied after dilution with water. Preferably, for various purposes
of end user application, a so-called aqueous spray-liquor is
prepared by diluting the compositions of the present invention with
water, e.g. tap water. The spray-liquors may also comprise further
constituents in dissolved, emulsified or suspended form, for
example fertilizers, active substances of other groups of
herbicidal or growth-regulatory active substances, further active
substances, for example active substances for controlling animal
pests or phytopathogenic fungi or bacteria, furthermore mineral
salts which are employed for alleviating nutritional and trace
element deficiencies, and nonphytotoxic oils or oil concentrates.
As a rule, these constituents are added to the spray mixture
before, during or after dilution of the compositions according to
the invention.
[0156] The compositions of the invention can be applied by the
pre-emergence or the postemergence method. If the saflufenacil is
less well tolerated by certain crop plants, application techniques
may be employed where the herbicidal compositions are sprayed, with
the aid of the spraying apparatus, in such a way that the leaves of
the sensitive crop plants ideally do not come into contact with
them, while the active substances reach the leaves of undesired
plants which grow underneath, or the bare soil surface
(post-directed, lay-by).
[0157] Depending on the aim of the control measures, the season,
the target plants and the growth stage, the compositions of the
invention are applied to such a degree that the application rates
of saflufenacil are from 0.001 to 3.0, preferably from 0.01 to 1.0
kg/ha active substance (a.s.).
[0158] To widen the spectrum of action and to obtain synergistic
effects, the compositions of the invention can be mixed with a
large number of representatives of other groups of herbicidal or
growth-regulatory active substances and applied together with
these. Examples of suitable mixing partners are 1,2,4-thiadiazoles,
1,3,4-thiadiazoles, amides, amino phosphoric acid and its
derivatives, amino triazoles, anilides,
aryloxy/heteroaryloxyalkanoic acids and their derivatives, benzoic
acid and its derivatives, benzothia diazinones,
2-(hetaroyl/aroyl)-1,3-cyclohexanediones, heteroaryl aryl ketones,
benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates,
quinolinecarboxylic acid and its derivatives, chloroacetanilides,
cyclohexenone oxime ether derivatives, diazines, dichloropropionic
acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones,
dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls,
halocarboxylic acids and their derivatives, ureas, 3-phenyluracils,
imidazoles, imidazolinones, N-phenyl3,4,5,6-tetrahydrophthalimides,
oxadiazoles, oxiranes, phenols, aryloxy- and
heteroaryloxyphenoxypropionic acid esters, phenylacetic acid and
its derivatives, 2-phenylpropionic acid and its derivatives,
pyrazoles, phenylpyrazoles, pyridazines, pyridine carboxylic acid
and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas,
triazines, triazinones, triazolinones, triazolecarboxamides and
uracils.
[0159] It is of also possible to use the compositions of the
present invention as a tank-mix partner with other formulations.
Thus, the compositions of the invention can be mixed and applied
together with a large number of different pesticide compound
formulations, for example those that include active ingredients or
adjuvants, such as atrazine, glyphosate, glufosinate,
S-metolachlor, 2,4-D ester, isoxaflutole, diflufenzopyr, dicamba,
mesotrione, dimethenamid-P, pendimethalin, imazethapyr, paraffin
oils, polyol fatty acid esters, polyethoxylated polyol fatty acid
esters, ethoxylated alkyl aryl phosphates, methylated seed oils,
emulsifiers, ammonium sulfate or mixtures thereof.
[0160] Moreover, it may be useful to apply the
saflufenacil-containing compositions of the invention, separately
or in combination with other herbicides, jointly as a mixture with
yet further plant protection agents, for example with agents for
controlling pests or phytopathogenic fungi or bacteria. Also of
interest is the miscibility with mineral salt solutions which are
employed for alleviating nutritional and trace element
deficiencies. Nonphytotoxic oils and oil concentrates may also be
added.
[0161] The present invention offers the following advantages:
[0162] It is easy and economical to carry out.
[0163] Compositions according to the invention are compatible with
a broad range of other pesticides and formulations thereof, in
particular herbicides with a solubility in water of at least one
g/l, such as auxins, bentazone, diquat and paraquat and their
formulations. In particular, the compatibility with dicamba,
glyphosate, glufosinate, MCPA, 2,4-dichlorophenoxyacetic acid,
2,4,5-Trichlorophenoxyacetic acid, bentazone, diquat and paraquat
and their formulations is achieved.
[0164] Compositions according to the invention show both high
physical and chemical stability over prolonged storage periods
while maintaining their biological efficacy.
[0165] Upon dilution with water, the compositions according to the
invention give stable aqueous compositions of saflufenacil and form
no or only little coarse material or supernatant liquid.
[0166] The following examples are intended to further illustrate
the present invention without limiting its scope in any way.
EXAMPLES
I. Analytics:
[0167] Particle size Distribution (PSD) was determined by statistic
laser scattering using a Malvern Mastersizer 200 according to
European norm ISO 13320 EN. The data were treated according to the
Mie-Theory by software using a "universal model" provided by
Malvern Instruments. Important parameters are the dn-values for
n=10, 50 and 90, the d10, d50 and d90.
[0168] Solid content of the final dispersion was measured by
evaporating the volatiles of small probe of the aqueous suspension
in an oven at 105.degree. C. for 2 hours. The value indicated for
the examples is an average value from three parallel
experiments.
II. Ingredients:
[0169] Defoamer 1: defoamer based on a silicone oil emulsion
Defoamer 2: antifoam emulsion comprising polydimethylsiloxane
Biocide 1: aqueous biocidal formulation comprising
Methylisothiazolinone and Chlor-methylisothiazolinone Biocide 2:
glycol based biocidal formulation comprising Benzisothiazolinone
Biocide 3: biocidal formulation comprising
2-Bromo-2-nitropropane-1,3-diol
Xanthan Gum
[0170] Adjuvant 1: methylated seed oil, alkylphenol ethoxylate
[0171] Nonionic Surfactant 1: nonionic surfactant comprising
tristyrylphenol alkoxylate [0172] Nonionic Surfactant 2: nonionic
surfactant of the type PEO-PPO-PEO, Mw of the PPO block 3250 g/mol,
percentage of polyethylenglycol on molecule 50 wt % Anionic
Surfactant A1-1: Sodium lignosulfonate, see table 1 Anionic
Surfactant A1-2: Sodium lignosulfonate, see table 1 Anionic
Surfactant A1-3: lignin, sulfomethylated, see table 1 Anionic
Surfactant A1-4: Sodium lignosulfonate, see table 1 Anionic
Surfactant A1-5: Sodium lignosulfonate, see table 1 Surfactant
A2-1: 20% aqueous solution of poly(2-acrylamido-2-methylpropane
sulfonic acid) sodium salt with pH 2.5-4; (CAS 55141-01-0 or
35641-59-9) Pre-condensate P1: 70% w/w aqueous solution of
etherified melamine formaldehyde pre-condensate, CAS 68002-20-0
[0173] Roundup.RTM. Powermax II Herbicide: commercially available
aqueous solution of glyphosate potassium, content 540 grams of
glyphosate per liter (calculated as glyphosate acid) [0174]
Engenia.RTM. Herbicide: commercially available aqueous solution of
the N,N,Bis-(3-aminopylamine)methylamine salt of dicamba, content
600 grams of glyphosate per liter (calculated as dicamba acid)
[0175] Roundup WeatherMAX Herbicide: commercially available aqueous
solution of glyphosate potassium, content 540 grams of glyphosate
per liter (calculated as glyphosate acid) [0176] Honcho.RTM. plus
Herbicide commercially available aqueous solution of the isopropyl
ammonium salt of glyphosate, content 356 grams of glyphosate per
liter (calculated as glyphosate acid)
III. Preparation of the Compositions of the Invention:
a) Suspension Premix
[0177] 4.1 kg saflufenacil tgai (97.5% purity) was subjected to
bead milling in an aqueous phase containing 80 g sodium lauryl
sulfate, 8.0 g of Biocide 1, 16.0 g of Biocide 2 and 6.4 g of
Biocide 3, respectively, 4.0 g Defoamer 1, 4.5 g citric acid and
3.78 kg water until the particle size has reached a d50 of 1.1
.mu.m according to static laser scattering. (Equipment: Malvern
3000, software: V3.63, scattering model: Fraunhofer, analysis
model: universal)
b) Capsule Premix
[0178] 280 g of above suspension premix was mixed with 52 g of a 20
w % solution of Surfactant A2-1, then 59 g of Precondensate P1, and
finally 32 g of a 10 w % aqueous solution of citric acid. This
premix was heated to +80.degree. C. upon stirring, kept at
+80.degree. C. for 2 hours, then cooled to room temperature. A
microcapsule suspension with d50=4.6 .mu.m resulted (Equipment:
Malvern 3000, software: V3.63, scattering model: Fraunhofer,
analysis model: universal)
c) Capsule Formulation
[0179] To 10 g of above capsule premix was added 0.5 g polymeric
surfactant according to the following table and the suspension
equilibrated by stirring for 30 minutes. Five stabilized capsule
formulations, CS1 to CS5, resulted.
TABLE-US-00001 TABLE 1 properties of Anionic Surfactants A1-1 to
A1-5 Degree of sul- fo-nation [mol Dispersing Mw SO3/kg ligno-
Inventive/ Example agent [g/mol] sulfonate] comparison CS1 Anionic
Sur- 43,000 1.9 inventive factant A1-1 CS2 Anionic Sur- 65,000 1.7
inventive factant A1-2 CS3 Anionic Sur- 10,200 1.5 inventive
factant A1-3 CS4 Anionic Sur- 3,100 2.9 comparison factant A1-4 CS5
Anionic Sur- 6,200 0.7 comparison factant A1-5
d) Miscibility Tests
[0180] To simulate tank-mixing by a farmer, 0.7 g of above CS1 to
CS5 each were dispersed in 100 ml CIPAC D water, then 2.1 ml of
Roundup Powermax II Herbicide was added, shaken and the mixture
allowed to age for 24 hours. Subsequently, the fluid was poured
onto a 150 .mu.m sieve, and the residue left on the sieve judged
visually.
TABLE-US-00002 Capsule formulation Sieve residues Conclusion CS1
traces miscible with glyphosate, applicable CS2 nil miscible with
glyphosate, applicable CS3 traces miscible with glyphosate,
applicable CS4 large residue Incompatible with glyphosate, not
applicable CS5 large residue Incompatible with glyphosate, not
applicable
e) Final Confirmation of Compatibility
Capsule Formulation CS6:
[0181] 700 g of the capsule premix described in paragraph b) were
finished with 1.6 g Biocide 2, 0.6 g Biocide 3, 0.8 g Biocide 1,
4.2 g Defoamer 2, 25 g Nonionic Surfactant 2, 50 g Anionic
Surfactant A1-3, 2.5 g Xanthan, 35 g ammonium acetate, 24 g 25%
aqueous ammonia, and 260 g water to form saflufenacil formulation
CS6.
[0182] Formulation CS6 was dispersed in 100 g CIPAC D water and
test additives added according to the following table, then the
aqueous suspensions could age for 2 hours, and were finally poured
onto a 150 .mu.m sieve. Again, the residue left on the sieve was
judged visually.
TABLE-US-00003 CS6 Sieve Run [g] Additive 1 [g] Additive 2 [g]
residue 1 0.7 Roundup Powermax II 3.2 -- -- traces Herbicide 2 0.7
Roundup Powermax II 3.2 Adjuvant 1 0.9 traces Herbicide (NH4)2SO4
1.0 3 0.7 Engenia Herbicide 1.2 -- -- traces 4 0.7 Engenia
Herbicide 1.2 Adjuvant 1 0.9 nil (NH4)2SO4 1.0 5 1.0 Roundup
WeatherMAX 3.2 -- -- nil Herbicide 6 1.0 Roundup WeatherMAX 3.2
Adjuvant 1 0.9 nil Herbicide (NH4)2SO4 1.0 7 1.0 Honcho plus
Herbicide 4.1 -- -- nil 8 1.0 Honcho plus Herbicide 4.1 Adjuvant 1
0.9 nil (NH4)2SO4 1.0
f) Capsule formulation CS7:
[0183] 700 g of the capsule premix described in paragraph b) were
finished with 1.6 g Biocide 2, 0.6 g Biocide 3, 0.8 g Biocide 1,
4.2 g Defoamer 2, 25 g Nonionic Surfactant 1, 50 g Anionic
Surfactant A1-2, 2.5 g Xanthan, 35 g ammonium acetate, 24 g 25%
aqueous ammonia, and 260 g water to form saflufenacil formulation
CS7.
[0184] Formulation CS7 was dispersed in 100 g CIPAC D water and
test additives added according to the following table, then the
aqueous suspensions could age for 2 hours, and were finally poured
onto a 150 .mu.m sieve. Again, the residue left on the sieve was
judged visually.
TABLE-US-00004 CS7 Sieve Run [g] Additive 1 [g] Additive 2 [g]
residue 1 0.7 Roundup Powermax II 3.2 -- -- nil Herbicide 2 0.7
Roundup Powermax II 3.2 Adjuvant 1 0.9 traces Herbicide (NH4)2SO4
1.0 3 0.7 Engenia Herbicide 1.2 -- -- traces 4 0.7 Engenia
Herbicide 1.2 Adjuvant 1 0.9 nil (NH4)2SO4 1.0 5 1.0 Roundup
WeatherMAX 3.2 -- -- nil Herbicide 6 1.0 Roundup WeatherMAX 3.2
Adjuvant 1 0.9 nil Herbicide (NH4)2SO4 1.0 7 1.0 Honcho plus
Herbicide 4.1 -- -- traces 8 1.0 Honcho plus Herbicide 4.1 Adjuvant
1 0.9 traces (NH4)2SO4 1.0
g) Capsule formulation CS8:
[0185] 700 g of the capsule premix described in paragraph b) were
finished with 1.6 g Biocide 2, 0.6 g Biocide 3, 0.8 g Biocide 1,
4.2 g Defoamer 2, 25 g Nonionic Surfactant 2, 50 g Anionic
Surfactant A1-1, 2.5 g Xanthan, 35 g ammonium acetate, 24 g 25%
aqueous ammonia, and 260 g water to form saflufenacil formulation
CS8.
[0186] Formulation CS8 was dispersed in 100 g CIPAC D water and
test additives added according to the following table, then the
aqueous suspensions could age for 2 hours, and were finally poured
onto a 150 .mu.m sieve. Again, the residue left on the sieve was
judged visually.
TABLE-US-00005 CS8 Sieve Run [g] Additive 1 [g] Additive 2 [g]
residue 1 0.7 Roundup Powermax II 3.2 -- -- traces Herbicide 2 0.7
Roundup Powermax II 3.2 Adjuvant 1 0.9 traces Herbicide (NH4)2SO4
1.0 3 0.7 Engenia Herbicide 1.2 -- -- nil 4 0.7 Engenia Herbicide
1.2 Adjuvant 1 0.9 traces (NH4)2SO4 1.0 5 1.0 Roundup WeatherMAX
3.2 -- -- nil Herbicide 6 1.0 Roundup WeatherMAX 3.2 Adjuvant 1 0.9
traces Herbicide (NH4)2SO4 1.0 7 1.0 Honcho plus Herbicide 4.1 --
-- traces 8 1.0 Honcho plus Herbicide 4.1 Adjuvant 1 0.9 traces
(NH4)2SO4 1.0
* * * * *
References